Method of making chloroform.



T. GRISWOLD, JR. & C. J. STROSACKER.

METHOD OF MAKING GHLOROFORM. APPLICATION FILED JULY 26, 1912.

Patented June 23, 1914.

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UNITED STATES PATENT OFFICE.

THOMAS GRISWOLD, JR., CHARLES J. STROSACKEB, OF MIDLAND,

ASSIGNORS TO THE MIDLAND CHEMICAL CORPORATION OF MICHIGAN.

COMPANY, or MIDLAND, MICHIGAN, A

METHOD OF MAmNG CHLOBIOFORM.

" Specification of Letters Patent.

Patented J une'23, 1914.

Application filed July 26, 1912: Serial No. 711,653.

ment in Methods of Making Ghloroform,

' of which.v the following is a specification,

the principle of the invention being herein explained and the best modein whichwe have'contemplated applying that principle, so astodistinguish it from other inventions.

The present invention, relating as indicated to the manufacture ofchloroform, has more particular regard to the improvement of theso-called Smith process,

March 1, 1904. Such, Smithprocess, in its entirety, involves the actionof heated sulfur upon heated carbon so \as to produce carbon bi-sulfid;the action of chlorin on sulfur, so as to produce sulfur chlorid, ordi-chlorid: the action of such chlorid upon carbon bi-sulfid so as toproduce carbon tetrachlorid; and finally the reduction of carbontetrachlorid so as to produce chloro form. r n

The present improvements are concerned more particularly still with thelast of the foregoing steps, such steps, as heretofore carried out,being effected by mechanical agitation of the tetrachlorid with waterand finely divided iron, or other metal, powdered iron beingspecifically referred to, in the patent above named,

In order that the temperature of the reaction may be vproperlycontrolled, it has been found necessary, in practice, that this finelydivided iron should be added in successive portions and not all at once;this because the reaction with the fine iron is so violent that a largeamount of heat is generated and excessive amounts of pounds thanchloroform are produced. If, on the other hand, more coarselygranulatediron be used; the reaction is then slow, and although a greaterpercentage yield is obtained, such slowing down of the reaction soreduces the capacity that but little output is obtained from theapparatus, while a great deal of material is tied up in process. It isalso advantageous to add all portions of the charge at one time. i i

The object of the present invention acas described in U. S. LettersPatent No. 753,325, dated I other com' cordingly is the elimination ofthe foregoing d fficulties, such invention, to this end, consisting ofthe steps hereinafter fully described and particularly pointed out inthe claims.

The annexed drawing and the following MICHIGAN,

description set forth in detail one approved method of carrying out theinvention, such disclosed mode, however, constituting but one of variousways in which the principle of the invention may be used.

In said annexed drawing: the single figure there appearing represents,in more or less diagrammatic form, one type of apparatus suitable forcarrying out the operation in question.

Such typical apparatus will be seen to comprise rotatable agitating drumor 'cylinder 1 provided with trunnions 2 mounted in suitable bearings 3,and further provided with a spaced shell or jacket 4 by means of whichthe agitating cylinder or drum proper, together with its contents, maybe maintained at any desired'temperature. The temperature-controllingfluid, usually water, is supplied and withdrawn by means of pipes 5 and6, respectively, that pass through the left hand trunnion. Instead ofsuch shell 4, forming a water jacket, the drum may be simply rotated ina liquid bath maintained at the proper temperature.

Connecting with the cylinder, or drum, through the right hand trunnion2, which is made hollow for this purpose, and a connecting pipe 7, is asuction pump 8, by means of which any desired degree of vacuum may bemaintained by such drum. This pump remove any vapors from they cylinderas fast as formed. The gases or vapors thus abstracted from the cylinderby the pump are passed through a suitable fractionating apparatus 9, andthence into a condenser 10, from which they, are finally collectedan asuitable receptacle (not shown).

It should be explained that neither the arrangement of apparatus justdescribed, nor the general method of withdrawing the form any part ofthe present invention, the

latter relating to the form' in which that portion of the chargeconsisting of the iron, or other metal, is introduced into saidcylinder.

is likewise adapted, as will be eyident, to

vapors arising from the reaction in the drum It has been found that bychargin the proper amount of fine iron or otherr nely or "other hardbodies of the proper specific ter as an intermediate reduction productof L avity and treatin the charge of carbon tetrachlorid therewith in a,rotating reaction vessel of the kind illustrated in the drawing, orequivalent apparatus, wherein a grinding effect may be secured, a verymuch more satisfactory ,reduction of the tetrachlorid is secured. For bythis method,

coarser, larger iron particles may be used t make up a considerableportion of the finely divided iron, and such particles will be u.gradually reduced in fineness by the action of the balls in the mill soas to permit of a W the form of particles; and subjecting such certaincontrol of the reaction, which would not be possible if the same amountof iron, all in a finel divided state, were initially introduced. llotonly may a coarser and considerably cheaper grade of iron borings beused in this method, but at the same time the ,output of the apparatusis raised by an appreciable amount.

The fine articles of iron which are present in a limited amount in thecharge, all of which is put in\the reaction vesse at one time,immediately react to reduce the tetrachlo d, and as these become spent,more fi e particles are produced by the grinding action of the ballsupon the coarser particles, and in this way the reaction is maintainedin a satisfactory. and uniform state of progress until its completion,or until enough of the tetrachlorid has been reduced to warrantdistilling the charge, where the distillation is intermittent. Theoperator is taught by xperience to regulate the charge so that by thetime'the iron is practicallyspent the major portion of the tetrachloridwill have been converted. to chloroform. It is at this stage of theprocess that the temperature of the bath is raised so as to distil overtheproduct; the latter, passing through the fractionating column, iscondensed and collected in suitable containers. With thearrangement ofapparatus illustrated in the drawing it is contemplated that suchdistillation may be carried on practically throughout the entire processof reaction, this being rendered possibleby operating under reducedpressure, wherebythe chloroform, despite its characthe tetrachlorid, maybe withdrawn continuously.

Other modes of applying the principle of our invention be employedinstead of change being made as regards the process herein explained,provided the step or steps stated by any one of the following claims orthe equivalent of such stated step or steps be employed.

We therefore particularly point out and distinctly claim as ourinvent1on:.

1. The method of manufacturing chloroform, which consists in reducingcarbon tetrachlorid by means of a metal in the presenceof water, suchmetal being introduced in the form of particles; and subjecting suchparticles to a grinding action during the progress of the reaction,whereby they are radually reduced in fineness.

term, which consists in reducing carbon erachloridby means of iron inthe presence of water, such iron being introduced in particles to agrinding action during the progress of the reaction, whereby they aregradually reduced in fineness.

3. The method of manufacturing chloroform, which consists in reducingcarbon tetrachlorid by means of iron in the presence of water, at leasta portion of such iron being introduced in the form of relatively coarseparticles; and subjecting said particl es to a grinding actionduring theprogress of the reaction, whereby they are reduced in fineness. a

4. The method of manufacturing chloro- 2. The method of manufacturingchloroform, which consists in agitating Water,

carbon tetrachlorid, and iron together, at least a ortion of such ironbeing in the form of relatively coarse particles, andgrinding materialbeing included therewith, whereby said particles are gradually reducedin fineness as the agitation continues.

5. The method of manufacturing chloroform, which consists in agitatingwater, carbontetrachlorid, and iron together, at least a portion of suchiron being 1n the form of relatively coarse particles, and a quantity ofhard bodies being included' therewith, whereby said particles aregradually reduced in fineness as the agitation continues.

6.'The method of manufacturing chloroform, which consists in agitatinwater, car- "bon tetrachlorid,'and iron toget er, at least a portion ofsuch iron being in the form of relatively coarse articles and a quantityof iron balls being included therewith, whereby said particles aregradually reduced in fineness as the agitation continues.

Signed by us this 23rd day of July, 1912.

. THOMAS GRISWOLD, J R.

CHARLES J? STROSACKER.

C. A. EWLAND, DARDERSON.

